Quaternary ammonium compounds



2,703,795 QUATERNARY AMMONIUM coMroUNns American Cyanamid Company, NewYork, N. Y., a corporation of Maine No Drawing. Application August2851953, Serial No. 377,247

4 Claims. (Cl. 260--97.5)

This invention relates to novel quaternary ammonium compounds and to aprocess of preparing the same.

The novel quaternary ammonium compounds may be represented by thefollowing general formula:

wherein R1 represents a hydrocarbon radical of a fatty acid containingat least 8 carbon atoms, R2 represents a Joseph Emmett Carpenter,Greenwich, COIIIL, assignor to hydrocarbon radical of a rosin acid, R3and R4 are members of the group consisting of methyl and ethyl radicals,n is an integer having the values of 2 to 10, inclusive, and X is amember of the group consisting of chlorine, bromine and iodine.

The new compounds are surface active agents and are highly useful ascationic flotation agents, textile assistate temperature of from about120 C. to 300 C. with t the elimination of water to produce the amidecondensate of the formula:

Ru RF-O O--NHC1.l':izn-N in which n, R1, R3 and R4 have the significancenoted above. I I

In the second stage, this fatty amide condensate is reacted with -arosin acid and'aii epiha-lohydrin. The epoxyiringsof the epihalohydrinopens and forms an ester linkage with the rosin acid, whilesimultaneously the ghailide reacts to form a quaternary ammonium saltwith the tertiary amine group in the fatty amide, condensate. Thereaction in the second stage is exothermic and takes place spontaneouslyat an initial temperature of about 75 C., the temperature thereafterrising, usually to a little over 100 C. It is advisable, however, inorder to insure completion of this reaction, to hold the reactionrnixture at about 100 C. for several hours, or at higher temperaturesfor shorter periods of time. Temperatures up to about 200 C. can beused, although dangenof discoloration and decomposition begins at aboutthis point.

A variety of higher fatty acids or derivatives may be employed forreaction with the dialkyldiaminc. The carbon chain length in the fattyacid is preferably from 8 to 30 carbon atoms, and the hydrocarbon chainmay be saturated or unsaturated. Representative higher fatty acids thatmay be used are lauric, palrnitic, stearic, oleic, ricinoleic, capric,myristic and mixtures of such acids. The esters of these acids,particularly the esters from methanol, ethanol, glycol and glycerol canbe advantageously used instead of the free acids. In such cases, the

respective alcohols will be liberated in the first-stage reaction withthe diamine and will be removed from the reaction mixture or notdepending on the r volatility. Consequently, mixtures of fatty acids andtheir glycerides .inbefore described.

2,703,795 Patented Mar. 8, 1955 such as those found in naturallyoccurring animal, vegetable and marine oils such as coconut oil, palmoil, cottonseed oil, linseed oil, soya bean oil, olive oil, peanut oil,fish oils, and fractions from the refining of these oils may beadvantageously used.

The rosin acids which may be used in the present process include abieticacid and its isomers, including hydrogenated and disproportionated typesas well as the naturally occurring varieties, such as gum and woodrosin.

In a preferred embodiment of the present invention, I prefer to use talloil as the source of both the fatty acids and the rosin acids. As isknown, tall oil, as produced as a Ivy-Product from sulfate papermanufacture, is composed of a mixture of rosin acids, fatty acids(principally oleic acid and linoleic acid), lignin and unsaponifiablematter. Crude tall oil generally contains a relatively large proportionof rosin acids, frequently as much as 50% rosin acids. Depending uponthe extent of purification, it is possible to obtain various purifiedfractions of tall oil where the rosin content may run as low as 10% Whentall oil is to be used as the source material of both fattyacids androsin acids, I may use any grade of tall oil,

that is, crude, distilled or hydrogenated, provided that in those casesin which the mol per cent of rosin acids exceeds that of the fattyacids, it will usually be advantageous to provide enough additionalfatty acid so that the proportion of fatty acid in the initial reactionmixture is equal to or exceeds that of the rosin acids.

When tall oil is used as a source of fatty acids as well as rosin acids,it is apparent that opportunity will be provided in the first stage ofthe reaction for the rosin acids as well as the fatty acids to reactwith the primary amino group of the diamine. It might be supposed thatsome rosin acids will be consumed in this reaction so that thecomposition of the final product will differ from that here- I havefound, however, that such is not the case because the rosin acids arevery much less reactive toward amines than are the fatty acids and,therefore, the latter will be consumed first. Moreover, in the usualandpreferred practice of this invention, the quantity ofdialkyldi'am-ine employed in the first step of the reaction is'chemically equivalent to the quantity of fatty acids in the-reactionmixture and, consequently, no difficulty is encountered in reactingsubstantially :all of the fatty acids while leaving substantially all ofthe rosin acids unreacted in the first .step,

than ,would be expected from the corresponding reactions employing,abietic acid and most commercial forms of rosin. The most plausibleexplanation appears to be that the rosin acidsof tall oil are isomers ofabietic acid which have been formed in the heat treatment during thewood cooking process, and which are relatively inert. However, 'by theuse of anepihalohydrin, whichis a very reactive chemical, to combinewith the fatty amide condensate and with the rosin acids of tall oil inthe second stage of reaction, it has been found that complete reactionof the rosin acids takes place very easily.

It is another advantage of this invention that the ester linkage, onceit has been formed by reaction of the rosin acids with theepihalohydrin, displays the same inertness and stability characteristicsof the original. rosin acids. For this reason, hydrolysis of the esterlinkage does not occur readily, and in applications where resistance tohydrolysis is of importance, the products of the present invention areabout equally as stable as cationic surface active agents obtained fromfatty acids and employing only amide linkages.

Among the epihalohydrins which can be utilized to form the quaternaryammonium compounds of the present invention are epichlorohydrin,epibromohydrin, epiiodohydrin.

The products of this invention are also very suitable starting materialsfor the preparation of a large class of surface active agents in whichthe hydroxy group formed by the opening of the epoxy ring is reactedwith other epoxy compounds, particularly ethylene oxide andpropylfractionating column leading to a amine were reacted as in Example1.

and 0.342 eq. of uncombined carboxylic acids. parts (0.356 eq.) ofepichlorohydrin and 44.1 parts conjunction with the following specificexamples in which the parts are by weight unless otherwise specified.

Example I 313.0 parts (1 eq.) of crude tall oil, (Saponification No.179.3, Acid No. 166.0, Rosin Acid No. 89.4, corresponding to a contentof 0.499 equivalent of rosin acids) and 54.0 parts (0.529 mol) of3-dimethylam1nopropylamine were mixed and heated in a flask equippedwith a distillation condenser. Distillation began at a pot temperatureof 165 C., and the reaction was stopped after 30 minutes at a pottemperature of 207 C., at which point distillation of water wascomplete. Potentiometric titration of a sample of the amide intermediatewith standard alcoholic HCl showed a basic amine content of 0.546equivalent, nearly all of which was dirnethylamino nitrogen with only avery minor amount of primary amino nitrogen. Rotentiometric' titrationof another sample with standard KOH in methanol showed a tree carboxylicacid content of 0.512 equivalent. 50.0 parts (0.530 eq.) ofepichlorohydrin were added to the amide intermediate at 56 C., a

spontaneous reaction taking the temperature to 127 C.

in 8 minutes, but without causing refluxing of epichlorohydrin. Themixture was then heated at 154 160 for 1 hour, and on cooling produced adark, sticky SOlld which dispersed in hot water, making a foamysolution.

.The fatty and rosin acids of hydrogenated tall oil show the samedilference in reactivity towardB-dirnethylammopropylamine as those ofordinary tall 011. Hydrogenated tall oil can be substituted for ordinarytall 011 with equal success.

. Example 2 289.6 parts (1 eq.) of distilled tall oil (SaponificationNo. 193.7, Acid No. 188.0, Rosin Acid No. 55.0, corresponding to acontent of 0.284 equivalent of rosin acids), and 73.0 parts (0.716 mol)of 3-dimethylaminopropyl- The distillation began at 175 C. and thereaction was completed after 45 minutes at a final pot temperature of250 C. The intermediate amide product was found by potentiqmetrlctitration to contain 0.696 eq. of basic amino mtrogeg (0.340 eq.) oftechnical benzyl chloride were added in separate steps with cooling inbetween. The mixture was thereafter held at 135-147 C. for 1 hour tomsurecompletion of the reaction. The final product was a reddish solidon cooling, and dispersed in hot water giving a foamy solution. i

"Thisexample illustrates a situation very common in "practice in caseswhere the proportion of rosin acids in 'the tall oil employed is lessthan that of the fatty acids. Instead of adding more rosin acid, theproportion of epihalohydrin can be adjusted to the quantity of unre--acted rosin acids present after the initial reaction, and there resultsa mixture consisting of the product of this example together with thesurplus fatty amide condensate. While in some cases it is satisfactoryto leave the surplus fatty amide condensate as it is, it will generallybe preferred to convert it also to a quaternary ammonium salt, byreaction with benzyl chloride as shown, or with additional epihalohydrinor with any of the various other quaternizmg agents known to the art.The order of addition of the epihalohydrin and the other quaternizingagents is ordinarily immaterial, and they may also be addedsimultaneously.

Example 3 214.7 parts (1 eq.) of coconut oil (Saponification No. 261.3)and 116.2 parts (1 mol) of Z-diethylaminoethylamine are heated togetherunder reflux ceased to take place, the final temperature being in excessof 230 C. The 3-acylarnidoethyldiethylamine so produced is cooled and302.0 parts (1 mol) of abietic acid are added, together with 134 partstertiary butyl alcohol to serve as a solvent. After the abietic acid hasbeen dissolved by warming and again cooling to about 50 C., 137.0 parts(1 mol) of epibromohydrin is added, and following the temperature risefrom spontaneous reaction, the mixture is heated to the refluxtemperature of the tertiary butyl alcohol for several hours. The finalprod uct has properties similar to the products of Examples 1 and 2.

I claim:

1. The process of preparing a quaternary ammonium compound of thefollowing general formula:

until refluxing has wherein R1 represents a hydrocarbon radical of afatty acid containing at least 8 carbon atoms, R2 represents ahydrocarbon radical of a rosin acid, R3 and R4 are members of the groupconsisting of methyl and ethyl radicals, n is an integer having thevalues of 2 to 10, inclusive, and X is a member of the group consistingof chlorine, bromine and iodine, which comprises reacting adialkyldiamine of the formula:

/Ra HaN-C nHIn N with a fatty acid at a temperature of from about C. to300 C. and then reacting the amide condensate so formed with a rosinacid and an epihalohydrin at a temperature not appreciably greater than200 C.

2. The process according to claim 1 in which the fatty acid and rosinacid are derived from tall oil.

3. The process according to claim 2 in which the dialkyldiamine isS-dimethylaminopropylamine.

4. The process according to claim 2 in which the epihalohydrin isepichlorohydrin.

References Cited in the file of this patent UNITED STATES PATENTS2,540,678 Kelley Feb. 6, 1951 2,636,028 Sommer et a1. Apr. 21, 19532,640,822 Harman et al- June 2, 1953

1. THE PROCESS OF PREPARING A QUATERNARY AMMONIUM COMPOUND OF THEFOLLOWING GENERAL FORMULA: WHEREIN R1 REPRESENTS A HYDROCARBON RADICALOF A FATTY ACID CONTAINING AT LEAST 8 CARBON ATOMS, R2 REPRESENTS AHYDROCARBON RADICAL OF A ROSIN ACID, R3 AND R4 ARE MEMBERS OF THE GROUPCONSISTING OF METHYL AND ETHYL RADICALS, N IS AN INTEGER HAVING THEVALUES OF 2 TO 10, INCLUSIVE AND X IS A MEMBER OF THE GROUP CONSISTINGOF CHLORINE, BROMINE AND IODINE, WHICH COMPRISES REACTING ADIALKYLDIAMINE OF THE FORMULA: